LnIII Complexes Displaying ErIII-centered Upconversion Emission in Solution and the Solid State with YbIII, NdIII or a Porphyrin-based ligand as Activators

LnIII 配合物以 YbIII、NdIII 或基于卟啉的配体作为激活剂在溶液和固态中显示以 ErIII 为中心的上转换发射

• 批准号: 2154848
• 负责人: Anne Gorden
• 金额: $ 65万
• 依托单位: Texas Tech University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-09-01 至 2025-08-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2154848&HistoricalAwards=false
• 关键词: LnIII; Complexes; Displaying; ErIII; centered

With the support of the Chemical Structure, Dynamics, and Mechanisms B (CSDM-B) program in the Division of Chemistry, Anne E. V. Gorden of Texas Tech University, Ana de Bettencourt-Dias of the University of Nevada, Reno, and Jorge Monteiro of California Polytechnic State University-Humboldt will study lanthanide complexes with erbium, ytterbium, and neodymium to develop new compounds that have the potential to display efficient upconversion emission both in the solid state and in solution. In two-photon upconversion, light of lower energy non-destructive wavelengths, such as infrared light, is converted to higher energy emission in the visible region of the electromagnetic spectrum through a materials-excitation mechanism. The development of these new metal complexes as water-soluble compounds is expected to enable their application as new luminescent probes for bio-imaging of cells in real time without the need to employ damaging, high-energy radiation. In the long term, such studies have the potential to open up new vistas for biomedical science, by providing enabling tools to study processes in cells and biological tissues without perturbing the biology. Such complexes might, for example, provide a new means of analyzing metabolic processes or the reactivity of metalloenzymes in living tissues, thereby introducing new readouts for both healthy cell biology and dysfunctional cell biology, as a possible diagnostic tool.While selected examples of Ln(III)-upconversion emission in the solid state exist, the parameters for efficient upconversion emission in solution are not well established. To probe these parameters, the Gordon research team will isolate multi-metallic Ln(III)-ion complexes with water-soluble naphthylsalophen-based ligands and pre-organized supramolecular structures and characterize their photophysical properties. Ln(III)-ions have characteristic line-like spectra with long-lived emission, which can be easily distinguished from background fluorescence. Importantly, toxicity and low cell penetrability are not inherent concerns with Ln(III)-complexes and the emission properties of these complexes are not dependent on their crystalline phase. To realize upconversion emission, a combination of Yb(III) and Er(III) or Nd(III) and Er(III) in the complexes is needed, requiring careful balance of the necessary stoichiometry. Using judiciously designed systems, Dr. Gordon and her team will tune the properties of the Ln(III)-ion complexes for improved solubility, biocompatibility, and photophysical properties. Optimally, such probes should be water-soluble, display high emission efficiencies at emission wavelengths that are easily discriminated from tissue and cell fluorescence, and should be excited at wavelengths that are not absorbed by or damaging to biological tissues. This work is expected to contribute to better understanding of the structure-luminescence relationship that leads to increased upconversion emission in the solid state and in solution. The insights gained from this work have the potential to help guide the design and development of effective new luminescent probes, ultimately for applications in biological imaging.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

With the support of the Chemical Structure, Dynamics, and Mechanisms B (CSDM-B) program in the Division of Chemistry, Anne E. V. Gorden of Texas Tech University, Ana de Bettencourt-Dias of the University of Nevada, Reno, and Jorge Monteiro of California Polytechnic State University-Humboldt will study lanthanide complexes with erbium, ytterbium, and neodymium to develop new compounds that have the在固态和溶液中显示有效的上转换发射的潜力。在两光子上的转换中，通过材料激发机制，在电磁光谱的可见区域中，较低能量非破坏性波长（例如红外光）被转化为较高的能量发射。这些新的金属复合物的发展作为水溶性化合物有望实时使用新的发光探针，无需采用破坏性，高能辐射。从长远来看，此类研究有可能通过提供能够研究细胞和生物组织中的过程而不会扰动生物学的工具来开辟新的生物医学科学远景。例如，这种复合物可能会提供一种分析活性组织中金属酶的代谢过程或反应性的新方法，从而为健康细胞生物学和功能障碍细胞生物学引入了新的读数，作为可能的诊断工具。在LN（III）（iii） - 功能中的固体状态中，参与方案均不在固定效果。为了探究这些参数，戈登研究团队将用水溶性萘基盐基酚基配体和预构造的超分子结构隔离多金属LN（III）离子配合物，并表征其光物理特性。 LN（III）离子具有具有长寿命发射的特征线样光谱，可以很容易地将其与背景荧光区分开。重要的是，毒性和低细胞渗透性并不是LN（III） - 复合物的固有关注点，而这些复合物的发射特性并不依赖于它们的结晶相。为了实现上转化的发射，需要在复合物中组合Yb（III），ER（III）或ND（III）和ER（III），需要仔细平衡必要的化学计量。使用明智的设计系统，Gordon博士和她的团队将调整LN（III）-ION配合物的特性，以提高溶解度，生物相容性和光物理性能。最佳地，此类探针应具有水溶性，在发射波长下显示出较高的发射效率，这些发射波长很容易区分与组织和细胞荧光，并且应在未因生物组织或损害的生物组织所吸收或损害的波长上激发。预计这项工作将有助于更好地理解结构发光关系，从而导致固态和溶液中的上转换发射增加。 这项工作从这项工作中获得的见解有可能帮助指导有效的新发光探针的设计和开发，最终用于生物成像中的应用。该奖项反映了NSF的法定任务，并被认为是值得通过基金会的知识分子优点评估来支持的，并具有更广泛的影响。